US4329441A - Process for the polymerization of allyl ammonium salts and the resulting products - Google Patents

Process for the polymerization of allyl ammonium salts and the resulting products Download PDF

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US4329441A
US4329441A US06/206,154 US20615480A US4329441A US 4329441 A US4329441 A US 4329441A US 20615480 A US20615480 A US 20615480A US 4329441 A US4329441 A US 4329441A
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substituted
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acid
allyl
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Peter Bergthaller
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen

Definitions

  • This invention relates to a process for the polymerisation of monomer mixtures containing allyl ammonium salts and to new polymers.
  • Copolymers containing in particular primary or secondary ammonium salt monomer units or the monomer units containing primary or secondary amino groups derived therefrom at higher pH-values are interesting for various applications. For example, they are of interest in applications where the primary or secondary amino group is required as a nucleophilic and, therefore, alkylatable or acylatable centre in a polymer skeleton, for example for introducing groups bearing functional groups or for introducing crosslinking bridges by reaction with bifunctional or polyfunctional alkylating agents or acylating agents or by polymeranalog carbonamide formation with carboxyl groups thereof or of another macromolecule.
  • crosslinking in dilute phase or under special conditions gives above all intracatenarily crosslinked and, hence, soluble copolymers, whereas crosslinking in more concentrated systems gives insoluble networks which provide the polymer layers based thereon with high mechanical and chemical stability.
  • polymers containing amino groups are of interest for applications where, depending on the pH-value of the ambient medium, the amino groups appear as charge carriers, for example in cationic mordants for periodically fixing anionic compounds in polymer layers, for example for the pH-dependent dyeing of binders in photographic layers.
  • polymers containing primary or secondary amino groups are of interest for all of those purposes where amino groups are required as complex-forming ligands with an affinity for heavy metals in a polymer molecule, for example for use as protective colloid for noble metals or transition metals in sol form, for improving the adhesion of polymer coatings to metal surfaces or for forming a coherent metal film in the currentless plating of surfaces.
  • the introduction of primary or secondary amino groups into a copolymer skeleton has a particularly marked effect upon the protective colloid properties with respect to substantially insoluble transition metal or noble metal compounds of semiconductor character.
  • Such compounds may be obtained in the form of particularly agglomeration-stable dispersions by precipitation in the presence of polymers containing amino groups.
  • Allyl amine and substituted allyl amines are known to be monomers which polymerise particularly sluggishly. Even in the form of salts of strong acids, they polymerise only slowly and incompletely.
  • One of the objects of the present invention is to provide a process for the polymerisation of allyl ammonium salts.
  • the object of the present invention is to provide a process by which allyl ammonium salts can be quickly copolymerised in a technically simple manner with rapidly and completely polymerising monomers, particularly those of the acryl type, in high yields and with complete incorporation of the allyl ammonium salt used.
  • the process is intended to provide largely uniform polymers.
  • Another object of the present invention is to provide a process by which it is possible to obtain solvent-free water-soluble copolymers containing allyl ammonium salt units in copolymerised form which are suitable for use as protective colloids for noble metal or noble metal salt dispersions.
  • a further object of the present invention is to provide a process by which it is possible to obtain substantially monomer-free solutions of copolymers which contain polymerised units of allyl ammonium salts.
  • a final object of the present invention is to provide new polymers.
  • This invention therefore provides (1) a process for the polymerisation of allyl ammonium salts wherein a compound corresponding to formula (I) below ##STR1## in which
  • R 1 and R 2 which may be the same or different represent hydrogen; an aliphatic, araliphatic or cycloaliphatic radical preferably containing from 1 to 20 carbon atoms which may optionally be substituted, more particularly by one of the following groups:
  • R 1 and R 2 may together form the ring members required to complete a 5- to 7-membered heterocyclic ring, more particularly a pyrrolidone, piperidine, perhydroazepine, morpholine or thiomorpholine ring which may be substituted,
  • R 3 , R 4 and R 5 which may be the same or different represent hydrogen, an alkyl group which may be substituted, more particularly a C 1 -C 4 -alkyl group, especially methyl; more particularly hydrogen;
  • A is an anion, preferably monofunctional or difunctional, more particularly the anion of a strong inorganic or organic acid, particularly chloride, alkane sulphonate, aryl sulphonate, trifluoroacetate, perfluoroalkanoate, perfluoroalkane sulphonate or the sulphonate group of a monomer present in copolymerised or copolymerisable form, and/or
  • R 3 represents
  • R 20 and R 21 which may be the same or different represent hydrogen; an alkyl group which may be substituted, more particularly containing from 1 to 12 carbon atoms and preferably from 1 to 4 carbon atoms; an aryl group which may be substituted, particularly phenyl; a hydroxy group; an alkoxy group; particularly containing from 1 to 12 carbon atoms, an aralkyl group, particularly a benzyl group;
  • R 20 and R 21 may together form a group-O-R 23 -O- where R 23 is an alkylene radical which may be substituted containing no more than 6 carbon atoms; a dialkyl amino group where the alkyl radical is in particular a C 1 -C 4 -alkyl radical or Cl;
  • R 22 represents hydrogen; an acyl radical which may be substituted, more particularly of an aliphatic carboxylic acid containing from 1 to 20 carbon atoms or of an aromatic carboxylic acid, especially acetyl, pivaloyl, butyryl, benzoyl; alkyl, particularly containing from 1 to 12 carbon atoms, a dialkyl amino group where the alkyl radical is in particular a C 1 -C 4 -alkyl radical,
  • X represents a single electron pair or an oxygen atom, X being an electron pair when none of the radicals R 20 to R 22 is hydrogen.
  • the polymerisation reaction is preferably carried out at temperatures in the range from 60° to 90° C. and, more particularly, at temperatures above 70° C.
  • R 1 , R 2 represent hydrogen
  • R 4 , R 5 represent hydrogen
  • R 3 represents -CH 2 N.sup. ⁇ H 2 R 1 Cl.sup. ⁇ ; CH 3 or H
  • Particularly preferred compounds corresponding to the formula (I) are allyl amine hydrochloride; allyl ammonium methane sulphonate; allyl ammonium trifluoroacetate; allyl ammonium benzene sulphonate; 3-allyl ammonium propane sulphonate; 4-allyl ammonium butane sulphonate; the allyl ammonium salt of 2-acrylamido-2-methyl propane sulphonic acid; the allyl ammonium salts of methacryloyl hydroxy ethane sulphonic acid; allyl ammonium methyl phosphonate; N-ethyl allyl ammonium ethyl sulphate; N-cyanoethyl allyl ammonium chloride; N-hydroxy ethyl allyl ammonium chloride; methallyl ammonium chloride or 2-methylene-1,3-bis-alkyl ammonium propane dichlorides.
  • the phosphorus is preferably present in the oxidation state of +3.
  • Particularly preferred compounds of formula (II) are phosphorus acid, its anhydrides, chlorides, ester chlorides and its monoesters or diesters; and trialkyl phosphites.
  • Other suitable compounds of formula (II) are phosphonous acids and their esters or ester chlorides and, finally, hypophosphorous acid and disubstituted phosphine oxides.
  • the amides of all the above mentioned acids may also be used.
  • diethyl phosphite ethylene phosphite (2-oxo(2H)-1,3,2-dioxaphosphonite); dibutyl phosphite; phenyl phosphonous acid; phenyl phosphonous acid butyl ester; PCl 3 ; hexamethyl phosphorous acid triamide and phosphorous acid trimorpholide.
  • dialkyl esters of acyl phosphonic acid Kabachnik, Rossijskaja; Izv. Akad. Nauk. SSSR 1965, 597
  • the diethyl ester of methacryloyl phosphonic acid of which the cleavage product, the methacrylic ester of the alcohol used as polymerisation medium, is incorporated into the polymer.
  • the invention provides:
  • the invention further provides:
  • Polymers corresponding to formula (III) may be obtained by polymerising compounds of formula (I) where R 3 is the group (--CR 4 R 5 --NR 1 R 2 H) + A, in the presence of a compound corresponding to formula (II).
  • Polymers produced in accordance with the invention may be in the form of ammonium salts or amines, depending on the pH value.
  • the monomer mixture to be polymerised may have any composition.
  • it preferably contains comonomers of the acryl type and may also contain comonomers containing electron donor groups in the molecule.
  • the proportion of these particular comonomers is preferably less than 20%, based on the acryl monomer, and less than 10%, based on all of the monomers.
  • neutral monomers such as styrene, may be copolymerised.
  • acrylamide acrylic acid-t-butyl amide; N-cyclohexyl acrylamide; methyl acrylate; ethyl acrylate; butyl acrylate; 2-hydroxy ethyl acrylate; 2-hydroxy propyl acrylate; acrylonitrile; acrylic acid; dimeric acrylic acid (3-acryloyl hydroxy propanoic acid); 2-acrylamido-2-methyl propane sulphonic acid; methacrylic acid; 2-hydroxy ethyl methacrylate; methyl methacrylate; methacrylonitrile; sulpho-ethyl methacrylate; itaconic acid, itaconic acid dimethyl ester; itaconic acid monobutyl ester; itaconic acid methoxy ethyl ester; itaconic acid mono-n-hexyl amide; N-sulphoethyl itaconic acid monoamide; male
  • N-vinyl-N-alkyl amides N-vinyl lactams; N-vinyl oxazolidinones; N-vinyl imidazoles; N-allyl imidazoles; N-methallyl imidazoles; vinyl sulphides; vinyl ethers; 1-acyloxy-2-acyloxy-2-methyl propenes; vinyl carboxylates; allyl ethers and the allyl ethers of aliphatic carboxylic acids;
  • the proportion of monomers of the allyl ammonium salt type corresponding to formula (I), based on all the monomers, during the copolymerisation reaction preferably amounts to at most 50 mole percent.
  • Copolymers of particular commercial interest contain from 5 to 30 mole percent of allyl ammonium salt units in copolymerised form, the remainder consisting of copolymerised monomers of the acryl type.
  • 2,518,622 di-tert.-butyl peroxide; tert.-butyl cumyl peroxide; dicumyl peroxide; 4,4'-di-tert.-butyl peroxy valeric acid-n-butyl ester; tert.-butyl peracetate; tert.-butyl perpivalate; tert.-butyl perbenzoate; tert.-butyl peroxy isopropyl carbonate; tert.-butyl peroxy-2-ethyl hexanoate; diisopropyl peroxy dicarbonate; dipropionyl peroxide; dioctanoyl peroxide; dilauroyl peroxide; dibenzoyl peroxide; dicyclohexyl peroxy dicarbonate; potassium persulphate; hydrogen peroxide; peracetic acid and monoperphthalic acid.
  • the type of initiator used is essentially determined by the polymerisation conditions
  • the optimum initiator may be determined by comparison tests.
  • the solvents used may be aqueous or non-aqueous systems.
  • the polymerisation medium does not have to be homogeneous. It is preferred to use solvents which dissolve all of the monomers.
  • the addition of regulating solvents, such as isopropanol, is occasionally favourable, although it may result in a reduction of yield and of average molecular weight.
  • Suitable solvents for carrying out the polymerisation reaction are any of the solvents normally used in the polymerisation field, above all those having relatively low chain transfer constants, for example water; tert. butanol; 2-methoxy ethanol; acetonitrile; ethyl acetate; 1,2-dimethoxy ethane; dioxane; 2-methoxy ethanol; benzene; chlorobenzene and o-dichlorobenzene. Mixtures of t-butanol with chlorobenzene in a ratio of from 1:10 to 10 are particularly favourable.
  • the average molecular weight of the polymers produced by the process according to the invention is preferably in the range from 20,000 to 400,000, although it is possible to obtain higher or lower molecular ranges, depending on the conditions selected.
  • the position of the average molecular weight depends on the quantity of initiator and on the proportion of phosphorus compound. Quantities of from 0.2 to 5 mole percent of phosphorus compound and from 0.05 to 2 mole percent of initiator, based on monomer, may be regarded as particularly favourable.
  • the phosphorus compound is generally used in a 1 to 10-fold molar excess, based on the initiator.
  • the polymerisation reaction is preferably carried out in the form of precipitation polymerisation, i.e. in a solvent which does not dissolve the polymer, and gives the polymers in the form of colourless and readily filterable powders which are easy to dry.
  • it may also be carried out by other methods, for example by solution polymerisation, the high degree of conversion obtained in the process according to the invention and, above all, the complete incorporation of the allyl ammonium salts making it possible for the polymer solutions to be used without further purification.
  • the polymers obtained show different properties which make them suitable for a variety of applications.
  • water-soluble, hydrophilic copolymers containing a very high proportion of acrylamide (up to 80%) and little or no hydrophobic monomers, for example butyl acrylate or 2-ethyl hexyl acrylate, are suitable for use as protective colloids for stabilising aqueous dispersions of hydrophobic constituents.
  • Monomer solution 42.6 g (0.6 mole) of acrylamide, 12.8 g (0.1 mole) of butyl acrylate, 10.8 (0.15 mole) of acrylic acid stabilised with 0.1% of butyl hydroquinone, 14.0 g (0.15 mole) of allyl ammonium chloride, 0.28 g of diethyl phosphite in 400 ml of t-butanol and 40 ml of chlorobenzene.
  • Monomer solution 39 g of acrylamide (0.55 mole), 12.8 g of butyl acrylate (0.1 mole), 17.2 g of methacrylic acid (0.2 mole); (freshly distilled over copper-acetate); 14.0 g of allyl ammonium chloride, 1.5 g of diethyl phosphite, 400 ml of t-butanol, 40 ml of chlorobenzene.
  • Monomer solution 39 g of acrylamide (0.55 mole), 12.8 g of butyl acrylate (0.1 mole), 17.2 g of methacrylic acid (0.2 mole), 14.0 g of allyl ammonium chloride, (0.15 mole), 400 ml of t-butanol, 40 ml of chlorobenzene.
  • the monomer solution is added under reflux in 10 portions over a period of 1 hour to a solution (intensively stirred under nitrogen) of 0.1 ml of tert.-butyl peroctoate in 100 ml of t-butanol and 10 ml of chlorobenzene, followed by refluxing for another hour. Only a few flakes of a greasy polymer are precipitated.
  • Example 4 shows that polymerisation only begins after the addition of the phosphorus compound and that it is only the added phosphorus compound which leads to the formation of a useful polymer.
  • Monomer solution 28.4 g (0.4 mole) of acrylamide, 25.6 g (0.2 mole) of butyl acrylate, 41.4 g (0.2 mole) of 2-acrylamido-2-methyl propane sulphonic acid, 11.4 g (0.2 mole) of allyl amine, 0.5 ml of 60% H 3 PO 2 , 500 ml of t-butanol.
  • Monomer solution 76.8 g (0.6 mole) of butyl acrylate, 41.4 g (0.2 mole) of 2-acrylamido-2-methyl propane sulphonic acid, 11.4 g (0.2 mole) of allyl amine, 0.4 ml of dimethyl phosphite, 500 ml of t-butanol.
  • Example 2 The procedure is as in Example 1, except that the polymer remains in solution and may be recovered in the form of a water-soluble syrup after concentration by evaporation in vacuo. Yield (as determined from the residue) 119 g (92% of the theoretical).
  • Monomer solution 49.7 g (0.7 mole) of acrylamide, 18.4 g (0.1 mole) of 2-ethylhexyl acrylate, 13 g (0.1 mole) of itaconic acid, 11.4 g (0.1 mole) of allyl amine-HCl, 0.3 ml of diethyl phosphite, 500 ml of t-butanol.
  • Monomer solution 25.5 g (0.5 mole) of acrylamide, 30 g (0.3 mole) of methyl methacrylate, 7.2 g (0.1 mole) of acrylic acid, 5.7 g (0.1 mole) of allyl amine, 17.2 g (0.1 mole) of anhydrous, p-toluene sulphonic acid, 0.4 g of phenyl phosphonous acid, 350 ml of t-butanol, 150 ml of chlorobenzene.
  • Monomer solution 60 g of ethyl acrylate (0.6 mole), 14.4 g of acrylate acid (0.2 mole), 22.8 g of allyl amine-HCl (0.2 mole), 300 ml of tert.-butanol.
  • Initiator solution 0.3 ml of t-butyl perpivalate, 0.5 ml of phenyl phosphinic, acid-n-butyl ester, 100 ml of t-butanol.
  • Receiving solution 0.1 ml of t-butyl peroctoate in, 100 ml of t-butanol.
  • the receiving solution is heated under nitrogen to reflux temperature. 1 quarter of the monomer solution and 1 quarter of the initiator solution are added under reflux with stirring at hourly intervals over a period of 4 hours. After refluxing for 4 hours, a total of 250 ml of t-butanol is distilled off under reduced pressure. Thereafter the ethyl acrylate odour has disappeared.
  • the viscous solution is made up with methanol to a total volume of 1000 ml.
  • Monomer solution 10 g of allyl amine.HCl 10 g of acrylamide, 5 g of acrylic acid, 50 mg of potassium metabisulphite, 50 ml of boiled, nitrogen-purged water.
  • Initiator solution 200 mg of potassium persulphate in, 50 ml of boiled water.
  • the monomer solution is added dropwise under nitrogen over a period of 60 minutes to the initiator solution kept at 38° C., after which the temperature is kept at 38° to 40° C. for 6 hours, followed by boiling.
  • the pH is then adjusted to 7 and the mixture is stirred into acetone (50 ml). After dissolution and reprecipitation, the copolymer is largely insoluble.
  • Monomer solution 10 g of allyl amine.HCl, 10 g of acrylamide, 5 g of acrylic acid,
  • Receiving solution 250 mg of azoisobutyronitrile in, 50 ml of tert.-butanol.
  • the polymer is highly soluble in water.
  • Receiving solution 0.1 ml of t-butyl peroctoate in, 50 ml of tert.-butanol.
  • the polymer is highly soluble in water.
  • copolymers 11 to 13 show clearly that the process according to the invention gives superior results.
  • the conventionally produced copolymer 11 is prone to crosslinking and unstable.
  • Monomer solution 31.8 g (0.6 mole) of acrylonitrile, 14.4 g (0.2 mole) of acrylic acid, 18.7 g (0.2 mole) of allyl amine.HCl, 0.4 ml of 60% H 3 PO 3 , 200 ml of t-butanol, 200 ml of chlorobenzene.
  • Monomer solution 35.5 g (0.5 mole) of acrylamide, 25.6 g (0.2 mole) of butyl acrylate, 10.8 g (0.15 mole) of acrylic acid, 14.0 g (0.15 mole) of allyl amine HCl, 0.3 ml of diethyl phosphite, 400 ml of t-butanol, 40 ml of chlorobenzene.
  • Monomer solution 49.7 g (0.7 mole) of acrylamide, 45.8 g (0.3 mole) of N-allyl glycine, hydrochloride, 0.3 ml of diethyl phosphite, 500 ml of t-butanol, 50 ml of chlorobenzene.
  • the product is dissolved in 200 ml of t-butanol and HCl is introduced into the resulting solution until its weight has increased by 20 g.
  • the hydrochloride is precipitated with chlorobenzene and taken up without drying in t-butanol.
  • Example 23a The procedure is the same as in Example 23a, except that a 37% methyl amine solution is used instead of ethylamine. Yield: 60 g (54% of the theoretical, Bp 105°-110° C.).

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US06/206,154 1979-11-17 1980-11-12 Process for the polymerization of allyl ammonium salts and the resulting products Expired - Lifetime US4329441A (en)

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Cited By (19)

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US4504640A (en) * 1982-05-19 1985-03-12 Nitto Boseki Co., Ltd. Process for producing monoallylamine polymer
US4514551A (en) * 1983-01-24 1985-04-30 Nitto Chemical Industry Co., Ltd. Process for the preparation of cationic polymers
US4540760A (en) * 1984-01-11 1985-09-10 Nitto Boseki Co. Ltd. Process for producing polymers of monoallylamine
US4569979A (en) * 1984-11-07 1986-02-11 Nitto Boseki Co., Ltd. Process for producing a polymer of an inorganic acid salt of monoallylamine
US4614593A (en) * 1985-03-28 1986-09-30 Ethyl Corporation Demulsification of oil-in-water emulsions
US4644042A (en) * 1984-09-01 1987-02-17 Nitto Boseki Co., Ltd. Polymers of N-substituted secondary monoallylamines and their salts and process for producing the same
US4657948A (en) * 1985-05-09 1987-04-14 Ethyl Corporation Fluid loss control in well cement slurries
US4661263A (en) * 1985-02-19 1987-04-28 Ethyl Corporation Water clarification
US4698380A (en) * 1985-09-23 1987-10-06 Ethyl Corporation Fluid loss control in well cement slurries
US4706755A (en) * 1985-05-09 1987-11-17 Ethyl Corporation Fluid loss control in well cement slurries
US4864007A (en) * 1986-07-02 1989-09-05 Sandoz Ltd. High molecular weight linear polymers of diallylamines and process for making same
US4927896A (en) * 1986-04-25 1990-05-22 Ethyl Corporation Process for polymerizing monoallylamine
US5629385A (en) * 1994-11-23 1997-05-13 Betzdearborn Inc. Allylamine copolymers having phosphonic, carboxylic or sulfonic groups and N-oxide derivatives thereof
US6268452B1 (en) * 1998-04-17 2001-07-31 Nitto Boseki Co., Ltd. Process for the production of allylamine polymer
US6303723B1 (en) 1998-10-28 2001-10-16 Penn State Research Foundation Process for polymerization of allylic compounds
US6407162B1 (en) * 1997-01-28 2002-06-18 Stepan Company Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids
US20040092632A1 (en) * 1997-01-28 2004-05-13 Stepan Company Antimicrobial polymer latexes derived from unsaturated quaternary ammonium compounds and antimicrobial coatings, sealants, adhesives and elastomers produced from such latexes
US20050010009A1 (en) * 1997-01-28 2005-01-13 Stepan Company, A Corporation Of The State Of Delaware Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids
US20050131080A1 (en) * 1997-01-28 2005-06-16 Stepan Company, A Corporation Of The State Of Delaware Ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids

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US4528347A (en) * 1983-11-10 1985-07-09 501 Nitto Boseki, Co. Ltd Process for producing polymers of monoallylamine
DE3434139A1 (de) * 1984-09-18 1986-03-20 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von carboxylgruppen enthaltenden polymerisaten
US5539820A (en) * 1994-10-06 1996-07-23 Northern Telecom Limited Protection of active telephone line interface circuits

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US2662875A (en) * 1952-02-20 1953-12-15 Chemstrand Corp Terpolymers of acrylonitrile and allyl amines
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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4504640A (en) * 1982-05-19 1985-03-12 Nitto Boseki Co., Ltd. Process for producing monoallylamine polymer
US4514551A (en) * 1983-01-24 1985-04-30 Nitto Chemical Industry Co., Ltd. Process for the preparation of cationic polymers
US4540760A (en) * 1984-01-11 1985-09-10 Nitto Boseki Co. Ltd. Process for producing polymers of monoallylamine
US4644042A (en) * 1984-09-01 1987-02-17 Nitto Boseki Co., Ltd. Polymers of N-substituted secondary monoallylamines and their salts and process for producing the same
US4569979A (en) * 1984-11-07 1986-02-11 Nitto Boseki Co., Ltd. Process for producing a polymer of an inorganic acid salt of monoallylamine
US4661263A (en) * 1985-02-19 1987-04-28 Ethyl Corporation Water clarification
US4614593A (en) * 1985-03-28 1986-09-30 Ethyl Corporation Demulsification of oil-in-water emulsions
US4657948A (en) * 1985-05-09 1987-04-14 Ethyl Corporation Fluid loss control in well cement slurries
US4706755A (en) * 1985-05-09 1987-11-17 Ethyl Corporation Fluid loss control in well cement slurries
US4698380A (en) * 1985-09-23 1987-10-06 Ethyl Corporation Fluid loss control in well cement slurries
US4927896A (en) * 1986-04-25 1990-05-22 Ethyl Corporation Process for polymerizing monoallylamine
US4864007A (en) * 1986-07-02 1989-09-05 Sandoz Ltd. High molecular weight linear polymers of diallylamines and process for making same
US5629385A (en) * 1994-11-23 1997-05-13 Betzdearborn Inc. Allylamine copolymers having phosphonic, carboxylic or sulfonic groups and N-oxide derivatives thereof
US6407162B1 (en) * 1997-01-28 2002-06-18 Stepan Company Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids
US20040092632A1 (en) * 1997-01-28 2004-05-13 Stepan Company Antimicrobial polymer latexes derived from unsaturated quaternary ammonium compounds and antimicrobial coatings, sealants, adhesives and elastomers produced from such latexes
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US6900265B2 (en) 1997-01-28 2005-05-31 Stepan Company Antimicrobial polymer latexes derived from unsaturated quaternary ammonium compounds and antimicrobial coatings, sealants, adhesives and elastomers produced from such latexes
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DE2946550A1 (de) 1981-05-27
EP0029169B1 (de) 1983-05-18
DE3063368D1 (en) 1983-07-07
EP0029169A2 (de) 1981-05-27
CA1165498A (en) 1984-04-10
JPS5682807A (en) 1981-07-06
EP0029169A3 (en) 1981-06-17

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